Glycerol ether mixture, cosmetic composition containing this mixture and process for its production

ABSTRACT

The invention relates to a glycerol ether mixture which consists essentially of a) at least one C 12-22  glycerol monoalkyl ether, b) at least one C 12-22  glycerol dialkylether and optionally c) at least one C 12-22  glycerol trialkyl ether and/or d) at least one C 12-22  fatty alcohol, components a) and b) together making up at least 50% by weight of the glycerol ether mixture and the ratio by weight of component a) to component b) being in the range from 3:1 to 1:2. The invention also relates to a process for producing the glycerol ether mixture and to cosmetic compositions containing the glycerol ether mixture.

RELATED APPLICATIONS

This application is a continuation of U.S. application Ser. No.11/121,392, filed May 4, 2005 which claims priority from GermanApplication No. 10 2004 022 252.5 filed May 4, 2004, the entire contentsof which are incorporated by reference.

BACKGROUND OF THE INVENTION

The use of glycerol monoalkyl ethers in cosmetic compositions is alreadyknown in principle. Thus, EP 0 599 433 A1 describes glycerolmonoalkylethers containing a C₆₋₁₈ and preferably a C₆₋₁₂ alkyl group asa deodorizing component in aqueous or alcoholic deodorant solutions. InDE 100 47 759 A1, C₆₋₁₈ glycerol monoalkyl ethers are used asantimicrobial components in wet wipes. In this case, too, the shorterchain glycerol monoalkyl ethers are preferred.

By virtue of their ether structure, partial glycerol ethers are stableto hydrolytic or catalytic degradation reaction by acidic antiperspirantsalts (aluminium or aluminium/zirconium salts) which is a very importantcriterion for their use as raw materials in the antiperspirant field.

Hitherto, glycerol ethers have acquired little significance asemulsifiers or consistency factors for cosmetic compositions. Inwater-containing antiperspirant/deodorant emulsions, fatty alcohols,such as cetearyl, stearyl and behenyl alcohol, fatty acid esters andalso triglycerides, such as glycerol monostearate, are normally used asco-emulsifiers or as consistency factors. By virtue of their chemicalstructure, fatty alcohols and hydroxyfatty acids are stable whereasfatty acid esters and triglycerides, such as glycerol monostearate, arenot.

The performance-related development of stable and viscosity-stable, butsensorially agreeable emulsions is a major challenge to the developer,particularly in the antiperspirant/deodorant field. The high saltcontent, the low pH and the fact that the antiperspirant componentsdissolved in water give rise to distinctly tacky end properties in theformulation call for new raw material solutions in the field ofantiperspirant/deodorant waxes in order to develop improvedantiperspirant/deodorant formulations.

Fatty alcohols, such as cetearyl, stearyl and behenyl alcohol, andhydroxyfatty acids, such as 12-hydroxystearic acid, in combination withthe polymeric N-acrylic acid amide are frequently used in water-freeantiperspirant stick and soft solid formulations (cf. U.S. Pat. No.5,429,816 A). Systems such as these do not always leave an optimalfeeling on the skin after application, even when optimized emollientsare used.

Accordingly, the problem addressed by the present invention was toprovide an emulsifier or consistency factor which would be suitable foruse over a broad range of applications and which, in the field ofaqueous o/w emulsions or solid cosmetic compositions and particularly inantiperspirant/deodorant formulations, would lead to stable productswith agreeable sensory properties.

BRIEF SUMMARY OF THE INVENTION

As a solution to the problems stated above, this invention provides anovel glycerol ether mixture having advantageous emulsifier andconsistency-imparting properties for cosmetic compositions including it,particularly antiperspirant compositions.

Accordingly, in a first embodiment, the present invention relates to aglycerol ether mixture which consists essentially of

a) at least one C₁₂₋₂₂ glycerol monoalkyl ether,

b) at least one C₁₂₋₂₂ glycerol dialkylether and optionally

c) at least one C₁₂₋₂₂ glycerol trialkyl ether and/or

d) at least one C₁₂₋₂₂ fatty alcohol,

components a) and b) together making up at least 50% by weight of theglycerol ether mixture and the ratio by weight of component a) tocomponent b) being in the range from 3:1 to 1:2.

DETAILED DESCRIPTION OF THE INVENTION

It has now surprisingly been found that a mixture consisting at least ofmono- and dialkyl ethers of glycerol in the particular ratio by weightmentioned above has extremely good emulsifying and consistency-impartingproperties. These properties are superior to those of the mono- ordialkyl ethers of glycerol used on their own. Particularly advantageousproperties are obtained when the ratio by weight of component a) (C₁₂₋₂₂glycerol monoalkyl ether) to component b) (C₁₂₋₂₂ glycerol dialkylether) is in the range from 1:1 to 1.3.1.

The glycerol ether composition according to the invention may consistsolely of components a) and b) mixed in the ratio mentioned above.However, C₁₂₋₂₂ glycerol trialkyl ethers (component c)) and/or C₁₂₋₂₂fatty alcohol (component d)) may also be present in themixture—generally from the production process. However, the predominantpart of the glycerol ether mixture consists of components a) and b)which, together, make up at least 50% by weight, more particularly morethan 60% by weight and, in a particularly preferred embodiment, morethan 70% by weight of the mixture. Besides components a) to d), smallamounts of other components may be present in the composition. Theseother components may also enter the mixture, for example, through theproduction process. Typical accompanying substances are, for example,water residues and impurities emanating from the raw materials used.Their percentage content in the claimed glycerol ether mixture is atmost 10% by weight and preferably at most 5% by weight. Accordingly, thewords “consists essentially of” in the context of the invention meanthat at least 90% by weight of the claimed glycerol ether mixtureconsists of components a) and b) and—where present—components c) and/ord).

The C₁₂₋₂₂ alkyl group of components a) to d) may be a saturated orunsaturated, branched or unbranched alkyl group. Suitable groups are,for example, cetyl, palmitoleyl, stearyl, isostearyl, oleyl, elaidyl,petroselinyl, linolyl, linolenyl, elaeostearyl, arachyl, gadoleyl,behenyl, erucyl and brassidyl. Technical mixture thereof, as obtainedfor example from natural fats and oils, may also be present.

C₁₆₋₁₈ alkyl groups, particularly saturated and unbranched types, areparticularly preferred.

Basically, each of the individual components of the glycerol ethermixture according to the invention may be separately prepared and thenmixed together in a suitable ratio. In such cases, the alkyl groups ofthe individual components may differ from one another. In a preferredembodiment, however, alkyl is the same for all components a) to d).Production is then preferably carried out so that the mixture ofcomponents a) and b) and optionally c) and d) is directly obtained fromthe reaction in the desired concentration distribution.

A particularly suitable (co)emulsifier or consistency factor in cosmeticcompositions is a glycerol ether mixture which consists essentially of35 to 45% by weight of component a), 25 to 45% by weight of componentb), 1 to 5% by weight of component c) and 8 to 27% by weight ofcomponent d). Even more preferred is a glycerol ether mixture whichconsists essentially of 40% by weight of component a), 30 to 40% byweight of component b), 2 to 3% by weight of component c) and 13 to 22%by weight of component d).

As already mentioned, the glycerol ether mixture according to theinvention is preferably produced so that the mixture of the individualcomponents in the desired quantities is obtained as the reaction productof the synthesis. A modification of the process described in applicants'WO 03/040072 A1 is particularly suitable. Here, the synthesis is mainlydirected towards the formation of monoalkyl ethers, the dialkyl ethersgenerally being formed in quantities of no more than 10% by weight andat most 16% by weight. In order to bring the ratio of mono- to dialkylethers into the range required in accordance with the invention and toincrease the percentage of more highly etherified products, thepercentage of glycerol in the educts is reduced by comparison with theExamples described in WO 03/040072 A1.

Accordingly, in the process according to the invention for theproduction of the glycerol ether mixture, as in the process according toWO 03/040072 A1, glycerol is deprotonated with a base and the waterformed is continuously removed from the reaction mixture, thedeprotonated glycerol is reacted with a component Z) selected from analkyl sulfate or a sulfuric acid alkyl ester and the solid phase formedand the aqueous phase are separated from the glycerol ether mixtureformed. In contrast to WO 03/040072 A1, however, the glycerol is used ina molar ratio of 4:1 to 2:1 to component Z). A ratio of glycerol tocomponent Z) of about 3:1 is particularly suitable for obtaining theparticularly preferred glycerol ether mixtures according to theinvention.

For all other process parameters, working up and purification steps,etc., reference may be made to WO 03/040072 A1.

In another embodiment, the present invention relates to a cosmeticcomposition which contains the glycerol ether mixture according to theinvention as an emulsifier and/or consistency factor.

The nature of the cosmetic composition is not particularly limited. Theglycerol ethers present in the mixture according to the invention aresolid, wax-like compounds. Accordingly, the glycerol ether mixture maybe incorporated in any cosmetic compositions which, hitherto, alreadycontained waxes, above all waxes with emulsifying orconsistency-imparting properties. Accordingly, suitable cosmeticcompositions range from water-free solid formulations, for example stickformulations (deodorant sticks, lipsticks, etc.) and semisolidformulations (so-called soft solids as used inter alia in deodorantpreparations) to aqueous emulsions (o/w emulsions for creams, lotions,roll-on deodorants, etc.).

The glycerol ether mixture according to the invention is particularlysuitable as an emulsifier or consistency factor in cosmeticcompositions. The components otherwise present in the cosmeticcompositions, such as emollients (oil components, fats, waxes), cosmeticor pharmaceutical active principles, thickeners, superfatting agents,fillers, dyes, pigments, stabilizers (antioxidants, preservatives), UVfilters, film formers, swelling agents, hydrotropes and perfume oils,may basically be used as before. Accordingly, they need not be discussedany further herein.

Particularly favorable results are obtained when the glycerol ethermixture makes up from 0.2 to 20% by weight and more particularly 0.5 to5% by weight of the cosmetic composition.

Whereas, basically, the glycerol ether mixture may be used as soleemulsifier or consistency factor, a preferred cosmetic compositioncontains the glycerol ether mixture in combination with at least oneother emulsifier and/or consistency factor. In this case, the quantityof the glycerol ether mixture depends on the other components used.Basically, however, the glycerol ether mixture makes up from 5 to 90% byweight, more particularly from 10 to 80% by weight and preferably from15 to 75% by weight of the total quantity of all emulsifiers.

Particularly good consistency-imparting properties for the cosmeticcomposition are achieved when the glycerol ether mixture according tothe invention is used in admixture with triglycerides, such ashydrogenated castor oil, with fatty alcohols, such as stearyl alcohol orbehenyl alcohol, or with hydroxyfatty acids, such as 12-hydroxystearicacid. The C₁₆₋₂₂ partial glycerol ethers in particular have a strongconsistency-imparting influence on various emollients and, accordingly,are most particularly suitable for water-free antiperspirant soft solidand stick formulations.

Over and above the pure consistency-imparting properties, extremelyhomogeneous inner structures and surface structures are obtained in thecosmetic formulation with the glycerol ether mixtures according to theinvention. With the high sensory demands antiperspirant products arebeing increasingly expected to satisfy by consumers in mind, the newglycerol ether mixture has a greatly improved influence on the overallsensory impression of the water-free final formulation. Thus, greaterskin smoothness and softness are obtained which leads to a distinctlyincreased skin-care impression of the formulation as a whole.

Even in water-based antiperspirant/deodorant emulsions, these waxes showvery favorable consistency-imparting properties through the build-up oflamellar phases which have proved to be extremely stable. Besidesimproved emulsion stabilities, increased viscosity stability in storageis also obtained. By virtue of the chemical structure of these partialglycerides and the lamellar structure ensuing therefrom, an extremelycaring, but also light overall sensory impression of the formulations onthe skin of the user is obtained. The partial glycerides also show verygood (co)emulsifying properties in PIT emulsions and thus provide verystable, thinly liquid emulsions.

Accordingly, a preferred application of the invention is in the field ofantiperspirant formulations. A particularly preferred cosmeticcomposition is distinguished by the fact that it contains at least onedeodorizing, astringent or antimicrobial compound.

The invention is illustrated by the following Examples.

EXAMPLES Example 1 Production of a Glycerol Ether Mixture According tothe Invention

In a 2-liter four-necked flask, 276 g (3 mol) glycerol were heated to120° C., 100 g (1.25 mol) 50% sodium hydroxide were slowly addeddropwise and the water formed was continuously removed by condensationat 120° C. under a vacuum of 100 mbar. Towards the end of the removal ofwater, the vacuum was reduced to 10 mbar. 380 g (1 mol) Lanette E powder(sodium cetyl stearyl sulfate powder) were added to and suspended in theNa gycerolate thus formed and the resulting suspension was stirred for 8h at 180° C. The reaction was monitored by determining the anionicsurfactant content which, after a reaction time of 8 hours, was wellbelow 1%. For working up, the reaction mixture was mixed with 225 mlwater and 5 ml 50% sodium hydroxide at a temperature of 90° C. and themixture was then left standing for phase separation. The phases formedwere then separated. To this end, the lower phase was filtered to removethe sodium sulfate precipitated and the upper organic phase (glycerolether phase) was washed with 250 ml water at a temperature of 90° C. Thephases were separated again. The organic phase was freed from water byvacuum distillation. The C_(16/18) glycerol ether mixture remained inthe distillation residue. The product contained ca. 40% by weightmono-C_(16/18)-glycerol ether, ca. 40% by weight di-C_(16/18)-glycerolether, ca. 2% by weight tri-C_(16/18)-glycerol ether and ca. 15% byweight C_(16/18) fatty alcohol.

Comparison Example 1 Preparation of a Glycerol Ether Mixture forComparison Purposes

A glycerol ether mixture containing glycerol monoether and diether in aratio of 1:4 was prepared as in Example using 0.5 mol instead of 3 molglycerol.

Formulation Examples Production of Cosmetic Compositions

Various cosmetic compositions were prepared using the glycerol ethermixture prepared in Example 1. Comparison formulations were additionallyprepared with the glycerol ether mixture of Comparison Example 1, thecorresponding monoglycerol ether and other typical emulsifiers orconsistency factors.

The compositions of the cosmetic preparations are shown in Tables 1 to 5below. Table 1 contains formulation examples for antiperspirant creamsand roll-ons, Table 2 contains formulation examples for skin-carecreams, Table 3 contains formulations for lipsticks, Table 4 containsformulation examples for sun creams and body and face care creams and,finally, Table 5 contains formulation examples for antiperspirant sticksand soft solids. The quantities in which the components are used areshown in % by weight. In the Tables, the Comparison Examples are denoted“C . . . ” and the Examples according to the invention are denoted “E .. . ”.

Some of the formulations were tested for their properties.

The viscosity measurements were carried out with a Brookfield RVFviscosimeter (spindle 5, 10 r.p.m.) for the formulations of Table 1 andwith a Brookfield RVT viscosimeter (spindle TE, 4 r.p.m. with Helipath)for the formulations of Table 2. The hardness measurements were carriedout with a Petrotest PNR 10 penetrometer from Petrotest Instruments GmbH& Co. KG (microcone: 5.0 g; drop bar: 47.5 g; measuring temperature: 23°C.; hardness=mm depth of penetration in 5 seconds).

The sensory tests were carried out by 4 trained testers. To this end,the formulations were applied to the forearm of the test person and thefollowing criteria were evaluated on a scale of −2 to +2: structure (−2:very inhomogeneous to +2: very homogeneous), viscosity stability andstability (−2: poor to +2: high), sensory impression (−2: poor to +2:very good) and oil secretion (−2: serious to +2: none). The results areset out in the following Table as averages of the individualevaluations.

TABLE 1 Antiperspirant creams and roll-ons Constituents INCI C1 C2 C3 C4C5 C6 C7 C8 Eumulgin B2 Ceteareth-20 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0Eumulgin B3 Ceteareth-30 — — — — — — — — Eumulgin S2 Steareth-2 — — — —— — — — Lanette O Cetearyl Alcohol 5.0 5.0 — — — — — — Lanette 22Behenyl Alcohol — — — — — — — — Cutina MD Glycerylstearate — — 5.0 5.0 —— — — C16/18-Monoglycerol ether 5.0 5.0 Glycerol ether mixture, Comp.5.0 5.0 Ex. 1, mono/di (1:4) Glycerol ether mixture, Ex. 1, — — — —mono/di (1:1) Cetiol S Diethylhexyl- 16.0 — 16.0 — 16.0 — 16.0 —cyclohexane Eutanol G16S Hexyldecyl — 16.0 16.0 — 16.0 — 16.0 StearateCetiol OE Dicaprylyl — — — — — — — — Ether Cetiol CC Dicaprylyl — — — —— — — — Carbonat Eutanol G Octyldodecanol — — — — — — — — DC 245Cyclomethicone — — — — — — — — Hydagen CAT Triethylcitrate — — — — — — —— Triclosan Triclosan — — — — — — — — Locron L Aluminum 40.0 40.0 40.040.0 40.0 40.0 40.0 40.0 Chlorohydrate Rezal 36 GC Aluminum — — — — — —— — Zirconium Chlorohydrate Glycerol Glycerine 3.0 3.0 3.0 3.0 3.0 3.03.0 3.0 Hydagen Chitosan — — — — — — — — DCMF Water Aqua to 100 to 100to 100 to 100 to 100 to 100 to 100 to 100 Preservation qs qs qs qs qs qsqs qs Viscosity [mPas] 15.000 20.000 7.000 9.000 1.000 1.000 15.00012.000 Structure +1 +1 +1 +1 0 0 +1 +1 Viscostability +1 +1 −1 −1 −2 −2−1 −1 Stability +1 +1 −2 −2 −2 −2 −1 −1 Sensory +1 +1 +1 +1 — — — —impression Constituents INCI E1 E2 E3 E4 E5 Eumulgin B2 Ceteareth-20 2.02.0 2.0 2.0 1.0 Eumulgin B3 Ceteareth-30 — — — — 1.0 Eumulgin S2Steareth-2 — — — — 1.0 Lanette O Cetearyl Alcohol — — 1.0 — — Lanette 22Behenyl Alcohol — — — — — Cutina MD Glycerylstearate — — 1.0 —C16/18-Monoglycerol ether Glycerol ether mixture, Comp. Ex. 1, mono/di(1:4) Glycerol ether mixture, Ex. 1, 5.0 5.0 4.0 4.0 2.5 mono/di (1:1)Cetiol S Diethylhexylcyclohexane 16.0 — 2.0 2.0 8.0 Eutanol G16SHexyldecyl Stearate — 16.0 2.0 2.0 2.0 Cetiol OE Dicaprylyl Ether — —4.0 4.0 — Cetiol CC Dicaprylyl Carbonat — — 4.0 4.0 2.0 Eutanol GOctyldodecanol — — 2.0 2.0 — DC 245 Cyclomethicone — — 2.0 2.0 2.0Hydagen CAT Triethylcitrate — — — — 1.0 Triclosan Triclosan — — — — 0.1Locron L Aluminum Chlorohydrate 40.0 40.0 40.0 40.0 Rezal 36 GC AluminumZirconium — — — — 40.0 Chlorohydrate Glycerol Glycerine 3.0 3.0 3.0 3.03.0 Hydagen DCMF Chitosan — — — — 0.05 Water Aqua to 100 to 100 to 100to 100 to 100 Preservation qs qs qs qs qs Viscosity [mPas] 40.000 40.00035.000 35.000 5.000 Structure +2 +2 +2 +2 +2 Viscostability +2 +2 +2 +2+2 Stability +2 +2 +2 +2 +2 Sensory impression +2 +2 +2 +2 +2

TABLE 2 Skin-care creams Constituents INCI C9 C10 C11 C12 E7 Emulgade PL68/50 Cetearyl Glucoside, 2.7 2.7 2.7 2.7 2.7 Cetearyl Alcohol Lanette OCetearyl Alcohol 1.6 — — — — Cutina MD Glycerylstearate — 1.6 — — —C16/18 Monoglycerol ether — — 1.6 — — Glycerol ether mixture, — — — 1.6— Comp. Ex. 1, mono/di (1:4) Glycerol ether mixture, — — — — 1.6 Ex. 1,mono/di (1:1) Myritol 331 Cocoglycerides 4.0 4.0 4.0 4.0 4.0 Cetiol OEDicaprylyl Ether 2.0 2.0 2.0 2.0 2.0 Cetiol V Decyl Oleate 2.0 2.0 2.02.0 2.0 Dimethicone DC 200 Dimethicone 0.5 0.5 0.5 0.5 0.5 Cetiol J600Oleyl Erucate 3.0 3.0 3.0 3.0 3.0 Glycerol Glycerine 3.0 3.0 3.0 3.0 3.0Water Aqua to 100 to 100 to 100 to 100 to 100 Preservation qs qs qs qsqs Viscosity [mPas] 50.000 60.000 <5.000 <10.000 140.000 Structure +1 +1+1 +1 +2 Viscostability −2 −1 −2 −2 +2 Stability +1 +1 −2 −2 +2 Sensoryimpression +1 0 — — +2

TABLE 3 Lipstick Constituents INCI E 8 Myritol 318 Caprylic/CapricTriglyceride 14.0 Myritol PC Propylene Glycol Dicaprylate/Dicaprate 6.0Eutanol G Octyldodecanol 17.0 Beeswax 8100 Cera Alba 5.0 (Carl&Co)Candelilla Wax Candelina cera 5.0 Carnauba Wax Carnauba cera 7.0Monomuls 90 L 12 Glyceryl Laurate 3.0 Dehymuls PGPH Polyglyceryl 2Dipolyhydroxystearate 4.0 Glycerol ether mixture, Ex. 1 8.0 Castor OilHydrogenated Castor Oil 10.0 Copherol F 1300 Tocopherol 2.0 Hydagen CMFChitosan Glycolate 10.0 Pigments as required

TABLE 4 Sun creams and body and face care creams Constituents INCI E9E10 E11 E12 E13 E14 Emulgade PL 6850 Cetearyl Glucoside, CetearylAlcohol 4.5 — — — — 5.0 Amphisol K Potassium Cetyl Phosphate 1.0 — — — —0.5 Cutina GMS Glyceryl Stearate — — — — — 0.5 Lanette O CetearylAlcohol — — — — 2.5 — Glycerol ether mixture, Ex. 1 1.0 1.0 1.5 3.0 3.03.0 Eumulgin VL 75 Lauryl Glucoside, Polyglyceryl-2 — 4.0 4.0 — 4.0 —Dipolyhydroxystearate, Glycerin Lanette E Sodium Cetearyl Sulfate — 1.01.0 — — — Emulgade SE-PF Glyceryl Stearate, Ceteareth-20, Ceteareth- — —— 5.0 — — 12, Cetearyl Alcohol, Cetyl Palmitate Eumulgin B1 Ceteareth-12— — — 1.0 — — Dimethicone DC 200 Dimethicone — — — 0.5 0.5 0.5 Cetiol OEDicaprylyl Ether 2.0 — — 2.0 Cetiol CC Dicaprylyl Carbonate — — 12.0 —4.0 5.0 Cetiol J600 Oleyl Erucate — — — — 2.0 — Cetiol SDiethylhexylcyclohexane — — — 1.0 — — Myritol 331 Cocoglycerides 8.012.0 10.0 — 2.0 — Cetiol B Dibutyl Adipate — 10.0 — — — — Cetiol 868Ethylhexyl Stearate — — — — — 4.0 Eutanol G16 Hexyldecanol 3.0 — — — — —Copherol 1300 Tocopherol 1.0 — — — 1.0 1.0 Cetiol SN CetearylIsononanoate — — — 2.0 — — Cegesoft PFO Passionflora Incarnata (EU),Passiflora — — — — — 2.0 Incarnata Seed Oil (non EU) Cegesoft PS6 Olus(EU), Vegetable Oil (non EU) — — — — — 3.0 Dow Corning 200 FluidDimethicone — — — 2.0 0.5 — Neo Heliopan, Type 303 Octocrylene 7.0 9.09.0 — — — Neo Heliopan, Type 357 Butyl Methoxydibenzoylmethane — — — 1.2— — Neo Heliopan, Type MBC 4-Methylbenzylidene Camphor 3.0 — — 1.0 — —Neo Heliopan AV Ethylhexyl Methoxycinnamate — 7.5 7.5 3.0 — — Zinckoxide NDM Zinc Oxide 7.0 5.0 — — — — Eusolex T 2000 Titanium Dioxide,Alumina, Simethicone — — 5.0 — — — Veegum Ultra Magnesium AluminiumSilicates 1.5 1.5 1.5 — — — Keltrol T Xanthan Gum 0.5 0.5 0.5 — — —Hispagel 200 Glycerin, Glyceryl Polyacrylate — — — 5.0 — — Carbopol 980(2%) Polyacrylate — — — — 15.0 — SFE 839 (GE Bayer Cyclopentasiloxane, —— — — 5.0 — Silicones) Dimethicone/Vinyldimethicone Crosspolymer Sepigel305 (Seppic) Polyacrylamide, C13-14 Isoparaffine, Laureth-7 — — — 1.0 —— Dry Flo Plus (Starch and Aluminium Starch Octenylsuccinate — — — — 5.0— Chemical Limited) Hydagen B Bisabolol — 0.05 0.5 — — — 1,3 ButyleneGlycol Butylene Glycol — — — — — 2.0 Glycerol Glycerine 3.0 3.0 3.0 —2.0 2.0 KOH (20% ig) Potassium Hydroxide — — — — 0.5 — Water,preservative to 100 to 100 to 100 to 100 to 100 to 100

TABLE 5 Antiperspirant sticks and soft solids Constituents INCI C13 C14C15 E15 E16 E17 E18 Lanette 18 Stearyl Alcohol 20.0 16.0 — — 4.0 —Cutina HR Hydrogenated Castor Oil — 4.0 — — 4.0 2.0 — 12-HydroxystearicAcid — — 12.0 — — — 8.0 GP1 — — — — — — — Glycerol ether mixture,Example 1 — — — 20.0 16.0 8.0 4.0 DC 245 Cyclomethicone 33.0 33.0 37.033.0 33.0 35.0 37.0 Cetiol OE Dicaprylyl Ether 9.0 9.0 10.0 9.0 9.0 10.010.0 Cetiol S Diethylhexylcyclohexane 15.0 10.0 18.0 10.0 15.0 18.0 18.0Arlamol E PPG15 Stearyether 2.5 2.5 DC 200 Dimethicone 2.5 2.5 Rezal 36GP Aluminum Zirconium 23.0 23.0 23.0 — — 23.0 — Tetrachlorohydrex GLYLocron P Aluminum Chlorohydrate — — — 23.0 23.0 — 23.0 Hardness(Penetration) 4.2 4.2 4.6 5.0 5.0 9.0 4.0 Structure 0 0 +1 +1 +1 +2 +2Stability −1 +2 +1 +2 +2 +2 +2 Oil secretion −1 +1 +1 +1 +1 +1 +1Sensory impression +1 +1 +1 +2 +2 +2 +2

What is claimed is:
 1. A glycerol ether mixture comprising a) at leastone C₁₂₋₂₂ glycerol monoalkyl ether, b) at least one C₁₂₋₂₂ glyceroldialkylether, c) optionally, one or more C₁₂₋₂₂ glycerol trialkyl etherand d) optionally, one or more C₁₂₋₂₂ fatty alcohol, wherein componentsa) and b) together make up at least 50% by weight of the glycerol ethermixture and the ratio by weight of component a) to component b) is inthe range from 3:1 to 1:2, and wherein components a) to d) make up atleast 90% of the mixture, based on the weight of the mixture.
 2. Theglycerol ether mixture according to claim 1, wherein the ratio by weightof component a) to component b) is in the range from 1:1 to 1.3:1. 3.The glycerol ether mixture according to claim 1, wherein C₁₂₋₂₂ alkylmeans a saturated or unsaturated, branched or unbranched alkyl group. 4.The glycerol ether mixture according to claim 1, wherein C₁₂₋₂₂ alkylmeans a saturated and unbranched, alkyl group containing 16 to 18 carbonatoms.
 5. The glycerol ether mixture according to claim 1, whereinC₁₂₋₂₂ alkyl is the same for all components a) to d), to the extent thatcomponents c) and d) are present.
 6. The glycerol mixture according toclaim 5, wherein C₁₂₋₂₂ alkyl means a saturated and unbranched alkylgroup containing 16 to 18 carbon atoms.
 7. The glycerol ether mixtureaccording to claim 1, comprising 35 to 45% by weight of component a), 25to 45% by weight of component b), 1 to 5% by weight of component c) and8 to 27% by weight of component d).
 8. A glycerol ether mixturecomprising a) 40% by weight of at least one C₁₂₋₂₂ glycerol monoalkylether; b) 30 to 40% by weight of at least one C₁₂₋₂₂ glyceroldialkylether; c) 2 to 3% by weight of one or more C₁₂₋₂₂ glyceroltrialkyl ether; and d) 13 to 22% by weight of one or more C₁₂₋₂₂ fattyalcohol; wherein components a) and b) together make up at least 50% byweight of the glycerol ether mixture and the ratio by weight ofcomponent a) to component b) is in the range from 3:1 to 1:2, whereincomponents a) to d) make up at least 90% of the mixture, based on theweight of the mixture, and wherein C₁₂₋₂₂ alkyl means a saturated andunbranched alkyl group containing 16 to 18 carbon atoms.
 9. The glycerolether mixture according to claim 1, wherein components a) to d) compriseat least 95% of the mixture, based on the weight of the glycerol ethermixture.